Two Channels of Electron Transfer Observed for the Reaction ofn-Butyl Chloride Parent Radical Cations with Naphthols and Hydroxybiphenyls

1998 ◽  
Vol 102 (29) ◽  
pp. 5754-5762 ◽  
Author(s):  
H. Mohan ◽  
R. Hermann ◽  
S. Naumov ◽  
J. P. Mittal ◽  
O. Brede
Keyword(s):  
Electron Transfer ◽  
Radical Cations ◽  
Butyl Chloride

Free electron transfer mirrors rotational conformers of substituted aromatics: Reaction of benzyltrimethylsilanes with n-butyl chloride parent radical cations

2004 ◽  
Vol 6 (9) ◽  
pp. 2267 ◽  
Author(s):  
Ortwin Brede ◽  
Ralf Hermann ◽  
Sergej Naumov ◽  
Antonios K. Zarkadis ◽  
Gerasimos P. Perdikomatis ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Free Electron ◽  
Radical Cations ◽  
Butyl Chloride

scholarly journals Spectral Probe for Electron Transfer and Addition Reactions of Azide Radicals with Substituted Quinoxalin-2-Ones in Aqueous Solutions

2021 ◽  
Vol 22 (2) ◽  
pp. 633
Author(s):  
Konrad Skotnicki ◽  
Slawomir Ostrowski ◽  
Jan Cz. Dobrowolski ◽  
Julio R. De la Fuente ◽  
Alvaro Cañete ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Aqueous Solutions ◽  
Absorption Spectra ◽  
Density Functional ◽  
Reduction Potential ◽  
Biological Significance ◽  
Radical Cations ◽  
Basis Sets ◽  
Double Bonds ◽  
Reduction Potentials

The azide radical (N3●) is one of the most important one-electron oxidants used extensively in radiation chemistry studies involving molecules of biological significance. Generally, it was assumed that N3● reacts in aqueous solutions only by electron transfer. However, there were several reports indicating the possibility of N3● addition in aqueous solutions to organic compounds containing double bonds. The main purpose of this study was to find an experimental approach that allows a clear assignment of the nature of obtained products either to its one-electron oxidation or its addition products. Radiolysis of water provides a convenient source of one-electron oxidizing radicals characterized by a very broad range of reduction potentials. Two inorganic radicals (SO4●−, CO3●−) and Tl2+ ions with the reduction potentials higher, and one radical (SCN)2●− with the reduction potential slightly lower than the reduction potential of N3● were selected as dominant electron-acceptors. Transient absorption spectra formed in their reactions with a series of quinoxalin-2-one derivatives were confronted with absorption spectra formed from reactions of N3● with the same series of compounds. Cases, in which the absorption spectra formed in reactions involving N3● differ from the absorption spectra formed in the reactions involving other one-electron oxidants, strongly indicate that N3● is involved in the other reaction channel such as addition to double bonds. Moreover, it was shown that high-rate constants of reactions of N3● with quinoxalin-2-ones do not ultimately prove that they are electron transfer reactions. The optimized structures of the radical cations (7-R-3-MeQ)●+, radicals (7-R-3-MeQ)● and N3● adducts at the C2 carbon atom in pyrazine moiety and their absorption spectra are reasonably well reproduced by density functional theory quantum mechanics calculations employing the ωB97XD functional combined with the Dunning’s aug-cc-pVTZ correlation-consistent polarized basis sets augmented with diffuse functions.

Surface photochemistry: Semiconductor mediated reactions of some 1,2-diarylcyclopropanes

1987 ◽  
Vol 65 (5) ◽  
pp. 976-979 ◽  
Author(s):  
Philip A. Carson ◽  
Paul de Mayo
Keyword(s):  
Electron Transfer ◽  
Radical Cations ◽  
Transfer Mechanism ◽  
Electron Transfer Mechanism ◽  
Trans Isomerization

1,2-Diphenylcyclopropane (1) was found to be oxidized on illuminated ZnO in the presence of air while 1-(p-methoxyphenyl)-2-phenylcyclopropane (2) and 1,2-bis(p-methoxyphenyl)cyclopropane (3) were found to be similarly oxidized on illuminated CdS. Compounds 2 and 3 were found, also, to undergo a rapid photochemical cis-trans isomerization on CdS whereas 1 did not undergo such isomerization. An electron transfer mechanism involving formation of the radical cations of the substrates is proposed.

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